N-(hydrocarbylthioalkyl)halophenoxy-acylamides as herbicides



United States Patent U.S. CI. 71-98 4 Claims ABSTRACT OF THE DISCLOSURE Applicant of an N- (hydrocarbylthioalkyl)halophenoxyacylamide as a preemergent and contact herbicide.

This is a division of application Ser. No. 518,012, filed Jan. 3, 1966.

This invention relates to organic compounds of halogen and nitrogen, and more particularly provides a new and valuable class of hydrocarbylthioalkyl nitrogen-substituted halophenoxyacylamides, the method of preparing the same, and the use of these compounds as biological toxicants.

According to the invention, the N-(hydrocarbylthioalkyl)halophenoxyacylamides are prepared by the reaction of a halophenoxyacyl halide with a hydrocarbylthioalkylamine as shown in the following equation:

wherein X and Y are halogens having an atomic weight greater than 30, R is a 'hydrocarbyl radical which is free of olefinic and acetylenic unsaturation and contains from 1 to 8 carbon atoms, m is an integer of from 1 to 5, n is an integer of from 1 to 3, and r is an integer of from 2 to 4.

Presently useful halophenoxyacyl halides are p-bromophenoxyacetyl chloride, 0 chlorophenoxyacetyl iodide, 11 chlorophenoxyacetyl bromide, 2,4 dichlorophenoxyacetyl chloride, 2,4 dibromophenoxyacetyl chloride, 2,4, trichlorophenoxyacetyl chloride, 2,4,6 trichlorophenoxyacetyl chloride, 2 (2,4 dichlorophenoxy)propionyl chloride, 2 (2,4 dichlorophenoxy)butyryl chloride, and 2 (2,4,5,6 tetraiodophenoxy)butyryl bromide. The preparation of a halophenoxyacyl chloride from a halophenoxyaliphatic acid and thionyl chloride is well known.

Presently useful hydrocarbylthiolakylamines are 2- (benzylthio)ethylamine, 2 (butylthio)ethylamine, l-ethylthio)ethylamine, 2-(methylthio)ethylamine, Z-(phenylthio)ethylamine, 2- (propylthio) ethylamine, 2-(p-tolylthio) ethylamine, 3 (benzylthio)propylamine, 3 (ethylthio) propylamine, 3 ethylthio) 3 (phenyl)propylamine, 3- (methylthio)propylamine, 2 (benzylthio)butylamine, 3- (benzylthio)butylamine, 3 (benzylthio) 3 (methyl) butylamine, and 3-(cyclohexylthio)propylamine.

N (hydrocarbylthioalkyl)halophenoxyacylamides provided by the invention are, for example:

N- [2- (butylthio) ethyl] -2- (p-bromophenoxy) acetamide,

N- [2- (ethylthio ethyl] (o-chlorophenoxy acetamide,

N- [2- (phenylthio ethyl] (p-chlorophenoxy acetamide,

N- 2- (benzylthio ethyl] -2- (2,4-dichlorophenoxy) acetamide,

'ice

N- [2- p-tolylthio ethyl] -2- 2,4,5 -trichlorophenoxy acetamide,

N- 3- (benzylthio propyl ]-2- (2,4,-dichlorophenoxy) acetamide,

N- L 3- (ethylthio propyl -2- (2,4-dichlorophenoxy) propionamide,

N- 3- (ethylthio -3- (phenyl propyl] -2- 2,4-dichlorophenoxy) butyramide,

N- 3- (benzylthio butyl -2- (o-chlorophenoxy) acetamide,

N- 3- (benzylthio -3- (methyl) butyl] -2- 2,4,5 ,6-tetraiodophenoxy) butyramide, and

N- 3- (cyclohexylthio propyl] -2- 2,4,-dibromophenoxy) acetamide.

Reaction of the halophenoxyacyl halide with a hydrocarbylthioalkylamine to give the presently provided N- (hydrocar-bylthioalkyl)halophenoxyacylamides is conducted by simply mixing the two reactants in substantially equimolar proportions and stirring until formation of said halophenoxyacylamide is completed. Advantageously, in order to obtain smooth reaction and optimum yield of the product, the reaction is conducted in the presence of an inert organic liquid diluent or solvent which may be, e.g., an aliphatic or aromatic hydrocarbon such as hexane, benzene or xylene, a chlorinated hydrocarbon such as chloroform, carbon tetrachloride or chlorobenzene, etc.

The reaction is generally exothermic; hence, heating is usually not required and the reaction may be conducted by operatin at ambient temperatures, or even with cooling. However, to shorten the reaction time for some of the somewhat sluggish acyl halides, heating may be used. Temperatures of from, say, 20 C. to C. are thus useful.

Since the reaction occurs with liberation of hydrogen halide, it is conveniently effected in the presence of a basic agent which will serve as hydrogen halide scavenger by forming a solid hydrohalide. Conveniently, an excess of the hydrocarbylthioalkylamine may be used for this purpose. However, it may be any organic or inorganic base which does not react with the halophenoxyacyl halide in preference to said amine, e.g., an alkali metal hydroxide or a basic salt thereof such as sodium, potassium, lithium or rubidium hydroxide, carbonate or acetate; an alkali rnetal alkoxide such as sodium or potassium methoxide or propoxide; a tertiary alkylamine such as trimethylamine or tributylamine, a heterocyclic nitrogne base such as N- methylrnorpholine or pyridine, a quaternary ammonium compound such as benzyltrimethylammonium methoxide or tetrabutylarnmonium butoxide, etc. An excess of the aromatic hydrocarbon amine is preferred.

Instead of using a hydrogen halide scavenger, or together with the scavenger, mechanical provision may be made for removal of the halide as it is formed, e.g., by means of vigorous stirring and/ or dephcgmation.

One mole of the halophenoxyacyl halide reacts with one mole of the said amine to give the present N-(hydrocarbylthioalkyl)halophenoxyacylamides; hence, the two reactants may be employed in such stoichiometric proportions. However, as above-stated, an excess of the aromatic hydrocarbon amine is conveniently used for the purpose of serving as scavenger for the by-product hydrogen halide. The resulting hydrohalide is readily removed from the reaction product by filtering or centrifuging, since it is insoluble in most organic solvents and in the reactants. Any excess of halophenoxyacyl halide or of the said amine may be separated by distillation or solvent extraction.

The N-(hydrocarbylthioalkyl)halophenoxyacylamidees are generally crystalline solids soluble in organic solvents such as ethanol, acetone, etc.

These novel compounds serve as preemergent and contact herbicides. For these purposes they can be dispersed as oil-in-water emulsions or mixed with inert fillers in a conventional manner, and the resulting herbicidal compositions are included within the scope of the invention. In the preparation of oil-in-water emulsions, ionic or nonionic wetting, dispersing or emulsifying agents are generally used, e.g., water-soluble salts of long-chain fatty acids; ethylene oxide condensates with fatty acids, alkyl prepared soil mixture and the pan leveled. The herbicidal composition was applied to the plantings prior to the watering of the seeds. This application of the herbicidal composition was made by spraying the surface of the soil with an acetone solution containing a sufficient quantity phenols and mercaptans; sulfonates of high molecular 5 ot the candidate chemical to obtain the desired rate per weight organic compounds, etc. For the preparation of acre on the soil surface. The watering of the seeds was powders, these compounds may be combined with inert accomplished by placing the aluminum pans in a sand substances such as talc, clays, tricalcium phosphate, cork bench having one-half inch depth of water thereon and dust, etc. These compounds may be used alone, or in permitting the soil in the pans to absorb moisture through admixture with other active carriers and additives includthe perforated bottom of the pans. ing fungicides, fumigants, bactericides, insecticides, ferti- The planted pans were thereafter placed on a wet sand lizers, hormones, or antibiotics. bench in a greenhouse and maintained there for 14 days In applying the herbicidal compounds, the concentraunder ordinary conditions of sunlight and watering. At tion and amount of active compound needed for killing 15 the end of this time, the plants were observed and the weeds without harming desirable plants are related to a results recorded by counting the number of plants of each number of factors including the species of plant, its stage species which germinated and grew. The herbicidal rating of growth, weather factors at the time of application was obtained by means of a fixed scale based on the and immediately following, etc. Dosage adjustments may average percent germination of each seed lot. The herbibe made by varying the concentration and/ or amounts of 0 cidal ratings are defined as follows: the herbicidal compositions employed, and may be determined by experimentation, as will be evident to one who 9 phywmxlClEY. is skilled in the art. F5119 PhYtOtOXlcltY Other uses for these novel compounds are as micro- 2 Moderate phytoiqxlclty biologicals, fungicides, plasticizers, and inhibitors. 3 Severe phytotoxlclty to i z Illustrated but not hunted The preemergent herbicidal activity of the compound of Example 1 is recorded in Table 1 for various application EXAMPLE 1 rates. In Table 1, the various seeds are represented by This example shows the preparation of N-[2-(benzylletters as follows: thio)ethyl]-2-(2,4-dichlorophenoxy)acetamide. A -General grass KFoxtail To a solution of 16.7 g. (0.1 mole) of 2-benzylthio- B Gene a1 broadleaf L Barnyard grass ethylamine and 10.1 g. (0.1 mole) of triethylamine in 150 C M ming glory M Crab grass ml. benzene was added slowly 24.0 g. (0.1 mole) of 2,4- D- Wild oat N-Pigweed dichlorophenoxyacetyl chloride. The mixture was stirred 13-13 grass O b an and cooled to maintain the temperature below 30 C. At F Rye grass P-Wild buckwheat the termination of the reaction, there was filtered off the G R di h Q Tomato theoretical quantity of triethylamine hydrochloride. Re- H Sugar beet R-Smghum moval of the benzene from the filtrate yielded a solid. Re- IC()tt()n S -Rice crystallization from methanol gave the product as needles, 4O J-C0rn melting at 87.5-89 C., in 93% yield. It analyzed as follows: General grass and general broadleaf were tested as Analysis.F0r C H CI NO S. Calcd. (percent): C. described above except that random mixtures of grass 55.14; H, 4.63; CI, 19.15; N, 3.78; S, 8.66. Found (perseeds and of broadleaf seeds were used. Barnyard grass, cent): C, 55.09; H, 4.70; Cl, 18.89; N, 3.77; S, 8.81. 5 cotton, corn and rice were similarly used in like tests.

TABLE 1 Plant type Rate,lbs./acreABCDEFGHIJKLMNOPQRS 1 "22101123 3 s23111 0.25 -0010oo0o100101o0200 0.05 0o10000o000100o0100 EXAMPLE 2 EXAMPLE 3 This example shows preemergent activity. This example shows activity as a contact herbicide. The preemergent herbicidal ratings of one of the com- The compound of Example 1 was applied in spray form pounds of the invention were determined in greenhouse to 21-day-old specimens of grasses and broadleaf plants. tests in which a specific number of seeds of 12 different The plants were grown in 9/2" x 5%" x 2%" pans from plants, each representing a principal botanical type, were five seeds of each of radish, morning glory and tomato; planted in greenhouse flats. A good grade of top soil was 10 seeds of each of sugar beet, sorghum and brome grass; placed in either 9 /2" x 5%" x 2%" or 9" x 13" x 2" 20 seeds of each of wild buckwheat, giant foxtail, rye aluminum pans and compacted to a depth of from grass, wild oat; approximately 20 to 30 of each of pigweed the top of the pan. On top of the soil were placed five and crab grass; and two soybean seeds in diagonally opseeds of each of radish, morning glory, and tomato; 10 posite corners. After the plants were 21 days old, each seeds of each of sugar beet, sorghum, and brome grass; 20 pan was sprayed with 6 ml. of a 0.5% concentration soluseeds of each of wild buckwheat, giant foxtail, rye grass, tion of the candidate chemical, corresponding to a rate wild oat; approximately 20 to 30 (a volume measure) of of approximately 9 lbs. per acre. This herbicidal solution each of pigweed and crab grass; and either 2 or 3 seeds was prepared from 1.5 ml. of a 2% solution of the canof soybean. The seeds were arranged with three soybean didate compound in acetone, 0.2 ml. of a cyclohexanoneseeds across the center of the large aluminum pan, the emulsifying agent mix and sufiicient water to make a monocotyledon or grass seeds scattered randomly over the remaining one-third of the soil surface, and the dicotyledon or broadleaf seeds scattered randomly over the remaining one-third of the soil surface at the other end of the pan. The seeds were then covered with of by dilution with Water. The injuries to the plants at the indicated concentrations of the test compound were then observed 14 days later and are reported in Table 2. The herbicidal ratings are defined as follows: no phytotoxicity; lslight phytotoxicity; 2moderate phytotoxicity; 3severe phytotoxicity; and 4-plant dead. The plant types are represented by letters as for Table 1.

6 an N-(hydrocarbylthioalkyl)halophenoxyacylamide of the wherein X is halogen having an atomic weight greater TABLE 2 Plant type Cone. wt. A B C D E F G H I J K L M N O P I Q R S 0 4 4 1 1 1 4 4 0 1 4 4 4 4 2 O 2 3 0 O 0 2 3 3 0 0 0 0 4 3 2 4 0 0 0 1 1 0 O 0 1 3 2 0 0 0 0 1 1 0 1 0 0 wherein X is halogen having an atomic Weight greater than 30, R is benzyl, m is an integer of from 1 to 4, n is an integer of from 1 to 3, and r is an integer of from 2 to 4.

2. The method of selectively inhibiting the germination of grass seeds in contact with soil and the preemergent growth thereof, which comprises treating the said soil with a herbicidal amount of an N-(hydrocarbylthioalkyl)halophenoxyacylamide of the formula wherein X is chlorine, R is benzyl, m=2, n=1, and r=2.

3. The method of controlling vegetation which comprises applying to the foliage a phytotoxic amount of a composition containing as the essential active ingredient than 30, R is benzyl, m is an integer of from 1 to 4, n is an integer of from 1 to 3, and r is an integer of from 2 to 4.

4. The method of controlling vegetation which comprises applying to the foliage a phytotoxic amount of a composition containing as the essential active ingredient an N-(hydrocarbylthioalkyl)halophenoxyacylamide of the formula 0 '-O(OH2)n NH(CH2)r sR )m wherein X is chlorine, R is benzyl, m=2, n=1, and r=2.

References Cited UNITED STATES PATENTS 2,577,969 12/1951 Jones 71-118 2,832,767 4/ 1958 Boettner 71118 3,141,758 7/1964 Hamm et a1. 7198 3,142,554 7/1964 Godfrey 71117 3,187,041 6/1965 Richter 71118 3,282,939 11/ 1966 Spivack et a1 260247.7 3,342,859 9/1967 Dorfman et a1 260-559 FOREIGN PATENTS 1,009,200 11/ 1965 Great Britain.

OTHER REFERENCES Geigy, Aryloxyacetarnides (1965), Belgium 659, 219, CA 64, pp. 2023-24 (1966).

LEWIS GOTTS, Primary Examiner G. HOLLRAH, Assistant Examiner US. Cl. X.R. 

